Ninova Silviya, Malcıoğlu Osman Barış, Auburger Philipp, Franke Matthias, Lytken Ole, Steinrück Hans-Peter, Bockstedte Michel
Chemistry and Physics of Materials, Paris-Lodron University Salzburg, Jakob-Haringer-Str. 2a, A-5020 Salzburg, Austria.
Theoretische Festkörperphysik, Friedrich-Alexander-Universität Erlangen-Nürnberg, Staudtstr. 7B2, D-91058 Erlangen, Germany.
Phys Chem Chem Phys. 2021 Jan 28;23(3):2105-2116. doi: 10.1039/d0cp04859c.
Porphyrins are key elements in organic-inorganic hybrid systems for a wide range of applications. Understanding their interaction with the substrate gives a handle on structural and electronic device properties. Here we investigate a single transition-metal porphyrin, namely Co(ii)-tetraphenylporphyrin (CoTPP), on the MgO(100) surface and the effect of multilayer film formation within hybrid density-functional theory and many-body perturbation theory. We focus on the relevant adsorption sites, simulate their photoemission spectra as a key fingerprint and compare with experiments on MgO(100) films on Ag(100). While we find only weak interaction between the cobalt centre and terrace sites on the MgO(100) surface, a strong interaction manifests itself with the low-coordinated sites. This leads to distinct features in both the valence and core-level regions of the electronic structure, as observed in the ultraviolet and X-ray photoemission spectra, corroborated by simulated spectra and calculated cobalt core-level shifts. Our work thus demonstrates the relevance of morphology-related low-coordinated sites and their properties in the adsorption of CoTPP on the MgO(100) surface.
卟啉是用于广泛应用的有机-无机杂化体系中的关键元素。了解它们与底物的相互作用有助于掌握结构和电子器件特性。在此，我们在混合密度泛函理论和多体微扰理论范围内，研究了MgO(100)表面上的单一过渡金属卟啉，即Co(ii)-四苯基卟啉（CoTPP）以及多层膜形成的影响。我们关注相关的吸附位点，模拟它们的光发射光谱作为关键指纹，并与Ag(100)上MgO(100)薄膜的实验进行比较。虽然我们发现钴中心与MgO(100)表面的平台位点之间只有微弱的相互作用，但与低配位位点存在强烈的相互作用。这导致了电子结构的价带和芯能级区域出现明显特征，如在紫外和X射线光发射光谱中观察到的那样，模拟光谱和计算出的钴芯能级位移证实了这一点。因此，我们的工作证明了与形态相关的低配位位点及其性质在CoTPP吸附在MgO(100)表面上的相关性。
